Phase-Transition Induced Elastic Softening and Band Gap Transition

Jul 12, 2013 - HiPSEC & Physics Department, University of Nevada, Las Vegas, Nevada 89154, United States. Inorg. Chem. , 2013, 52 (15), .... The refin...
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Phase-Transition Induced Elastic Softening and Band Gap Transition in Semiconducting PbS at High Pressure Shanmin Wang,†,‡,§ Jianzhong Zhang,† Yi Zhang,§ Andrew Alvarado,§ Jeevake Attapattu,§ Duanwei He,*,‡ Liping Wang,§ Changfeng Chen,§ and Yusheng Zhao*,†,§ †

LANSCE Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States Institute of Atomic & Molecular Physics, Sichuan University, Chengdu 610065, China § HiPSEC & Physics Department, University of Nevada, Las Vegas, Nevada 89154, United States ‡

S Supporting Information *

ABSTRACT: We have investigated the crystal structure and phase stability, elastic incompressibility, and electronic properties of PbS based on high-pressure neutron diffraction, in-situ electrical resistance measurements, and first-principles calculations. The refinements show that the orthorhombic phase is structurally isotypic with indium iodide (InI) adopting a Cmcm structure (B33). The cubic-to-orthorhombic transition occurs at ∼2.1(1) GPa with a 3.8% volume collapse and a positive Clausius−Clapeyron slope. Phase-transition induced elastic softening is also observed, which is presumably attributed to the enhanced metallic bonding in the B33 phase. On the basis of band structure simulations, the cubic and orthorhombic phases are typical of direct and indirect semiconductors with band gaps of 0.47(1) and 1.04(1) eV, respectively, which supports electrical resistivity measurements of an abrupt jump at the structural transition. On the basis of the resolved structure for B33, the phase transition paths for B1→B33→B2 involve translation of a trigonal prism in B1 and motion of the next-nearest neighbor Pb atom into {SPb7} coordination and subsequent lattice distortion in the B33 phase.

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INTRODUCTION

24. Elucidation of structural transition between B1 and B2 is thus of fundamental and technological importance. The structure of intermediate phase is a key to understanding the pressure-induced B1→B2 transitions. In most material systems the B1−B2 transition proceeds without involvement of any intermediate phase.24 As exceptions, only a few materials have an intermediate phase. Hexagonal structures, for example, have been reported for the B1→B2 transitions in AgF and NpAs.25,26 An isostructural transition is observed for SmTe and EuO before transforming to B2 modifications at higher pressures.27 For the cases of lead chalcogenides PbX (X = S, Se, and Te), the GeS-type (B16, Pnma or Pbnm (No. 62))3,11 and InI-type (B33, Cmcm (No. 63))8,12 structures have both been reported as intermediate phases on the basis of highpressure synchrotron X-ray diffraction (XRD). On another note, the B1→B16 (e.g., in NaBr and NaI)28 and B33→B2 phase transitions (e.g., in TlI and AgCl)29,30 are also observed at high pressures, implying that both B16 and B33 structures are likely candidates for the intermediate phase. However, as pointed out by Knorr et al.,12 a conclusive resolution of crystal structure between the two structure models is intrinsically difficult based on high-P XRD measurements, primarily because

Lead chalcogenides PbX (X = S, Se, and Te) are a class of technologically important semiconductors with narrow band gaps that have widely been used in infrared detectors, diode lasers, thermoelectric devices, and thermophotovoltaic converters.1−3 Anomalous ferroelectric fluctuations4,5 and giant anharmonic phonon scattering5,6 in PbX have recently been discovered and are theoretically attributed to competitive bonding between ionicity and covalency.7 At atmospheric pressure, these chalcogenides crystallize in a common NaCltype (B1) structure. They transform into a CsCl-type (B2) phase at 13.0−21.5 GPa from an orthorhombic (orthor) phase, typically found at lower pressures of 2.2−6.0 GPa.8−15 Interestingly, pressure-induced B1→orthor→B2 structural transitions are correlated with electronic transitions of semiconductor → semiconductor → metal.3,14 However, it is experimentally challenging to accurately determine electronic properties of the orthorhombic and B2 phases at high pressures; as a result, they have been the subject of debate and controversy.3,14,16−18 In fact, pressure-induced phase transition between B1 and B2 structures has also been observed in binary pnictides (e.g., CeP and CeAs),19,20 halides (e.g., NaCl and KCl),21 and hydrides (e.g., NaH and KH).22,23 A thorough overview of the B1→B2 transition can be found in ref © 2013 American Chemical Society

Received: April 1, 2013 Published: July 12, 2013 8638

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of significant overlap and broadening of Bragg reflections. Complicating matter further is that a new orthorhombic phase, neither of GeS- and InI-type structures, has been reported as an intermediate phase in PbTe at 6 GPa.9 Previous first-principles calculations on the structures of the orthorhombic phase have also been performed, but the results are as conflicting as the experimental reports.17,18,31,32 In addition, there are significant discrepancies in the elastic bulk modulus (K0) determined for orthorhombic PbS. The K0 value measured by Grzechnik et al., for example, is 134(2) GPa,13 which is more than 300% larger than that reported by Knorr et al. (30.9(4) GPa).12 A similar discrepancy can also be found in ab initio simulations.12,31 To date, all these controversies have yet been resolved for the orthorhombic phase, calling for more rigorous investigation into its structural, elastic, and electronic behaviors. In this work, we carried out high-pressure time-of-flight neutron diffraction, in situ electrical resistance measurements and first-principles calculations on PbS to study its crystal structures, phase stability, elastic and electronic properties. We also proposed new mechanisms for pressure-induced B1−B2 phase transition in PbS.

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Figure 1. Observed and refined time-of-flight neutron diffraction patterns of PbS at selected high P−T conditions. (a) Collected at ambient conditions. The observed diffraction lines for graphite are attributed to the graphite heater. (b) At room temperature and 2.1(1) GPa. The cubic-to-orthor transition occurs at ∼2.1(1) GPa with two PbS phases coexisting up to ∼3.7(1) GPa. (c) At room temperature and 3.7(1) GPa. In both (b) and (c), diffraction lines of diamond originate from polycrystalline diamond compact in toroidal-anvil cell.22 (d) At 2.4(1) GPa and 673 K. The orthorhombic PbS is completely back-transformed into the cubic phase. Red circles and black lines denote the observed and calculated profiles, respectively. The difference curves between observed and calculated pattern are shown in cyan. The tick marks correspond to the peak positions.

EXPERIMENTAL METHODS

High-purity commercially available PbS (>99.99%, ∼50 μm) powders were used for high-pressure (P) and high-temperature (T) neutron diffraction experiments. The time-of-flight experiments were performed in a TAP-98 toroidal-anvil press at Lujan Neutron Scattering Center, Los Alamos Neutron Science Center.33 Before the experiments, the sample powders were compacted into a cylindrical pellet of 5 mm in diameter and 8 mm in height. A sodium chloride (NaCl) capsule was used to isolate the pellet from the graphite furnace and also served as internal pressure standard. The pressure was determined using a Decker scale of NaCl,34 and the temperature was measured by a W5%Re−W26%Rh thermocouple. The experimental details were described in ref 33. To minimize nonhydrostatic stress built up during room-temperature compression, the sample was annealed at 623 K for 10 min at each experimental pressure before quenching to and collecting data at room-temperature. The obtained neutron diffraction patterns were refined by using a GSAS software.35 In situ electrical resistance measurement was carried out in a DS 6 × 8 MN cubic press installed at Sichuan University, China.36 A precompacted cylindrical pellet (1 mm in diameter and 2.5 mm in height) was surrounded by hBN pressure-transmitting medium. The electrical connections for resistance measurement are similar to those described in ref 37. At several desired temperatures, electrical resistance data were collected in the pressure range of 0.5−5.0 GPa at a rate of ∼0.2 GPa·min−1. The cell pressure was pre-calibrated by ex situ methods.36 A chromal-alumal thermocouple was used to monitor the sample temperature. Experimental details can be found elsewhere.36 First-principles calculations were performed for PbS using the generalized gradient approximation (GGA-PBE) implemented in the VASP package.38 The projector augmented-wave (PAW) and pseudopotential methods were employed with a plane-wave basisset, which was truncated at the cutoff energy of 400 eV to obtain a 0.2 meV convergence in the total energy per atom.39 The Brillouin zone integration was carried out with a 16 × 16 × 16 k-point grid generated by the Monkhorst−Pack algorithm.40 The final energy convergence for electronic steps is in the magnitude of 1 μeV. The force convergence of ionic steps was set to be 10 μeV/Å. The spin-orbital interaction was involved for band structure calculations.

values.3,8,11−15 Upon further compression, the relative intensity of orthorhombic phase increases, and at ∼3.7(1) GPa the cubic phase is completely transformed into orthorhombic PbS, as shown in Figure 1c. For comparison, the coexistence of cubic and orthorhombic phases was previously reported between 2.5 and 6.0 GPa by Knorr et al. based on high-P XRD measurements.12 This is because in our experiment the sample was subjected to high-T annealing before the data collection (see Experimental section for detail), which leads to enhanced kinetics for the cubic-to-orthorhombic transition. To further investigate high-T stability of the orthorhombic phase, we collected neutron diffraction patterns at high temperature. As shown in Figure 1d, the orthorhombic phase disappears at 2.4(1) GPa and 673 K, indicating that the cubic-orthorhombic transition boundary has a positive Clausius−Clapeyron slope. To determine the crystal structure of the orthorhombic phase, we refine the neutron diffraction pattern collected at 3.7(1) GPa (Figure 1c). Le Bail fitting is initially carried out to refine lattice parameters for both B16 and B33 structures in advance of Rietveld refinements. The refined results are a = 4.02 (1) Å, b = 11.12 (1) Å, and c = 4.22 (1)Å for Cmcm structure, and a = 11.03 (1) Å, b = 4.23 (1) Å, and c = 4.01 (1) Å for Pnma. Also noted is that the observed pattern can be fitted very well by using either of Cmcm or Pnma structure. However, Rietveld refinements of the Pnma structure show a large misfit with Rwp = 13.4% (the weighted profile R-factor) and χ2 = 7.7 (goodness of fit). For the Cmcm structure, the values of Rwp and χ2 are significantly reduced to 6.5% and 2.2, respectively. Figure 2 shows neutron diffraction patterns calculated for both Pnma and Cmcm PbS. Obviously, there is some mismatch between the calculated and observed diffraction lines for Pnma phase, especially at d-spacing of 2.9 and 3.3 Å. In this simulation the cation and anion positions are fixed respectively at 4c (0.1221, 1/4, 0.3723) and 4c (0.3495, 1/4,

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RESULTS AND DISCUSSION Figure 1 shows typical neutron diffraction patterns collected at high-P-T conditions. At room temperature, the onset pressure for the cubic-to-orthor transition is determined to be 2.1(1) GPa (see Figure 1b), which agrees well with previously reported 8639

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Table 1. Summary of Structural Parameters for Orthorhombic PbS Refined from the Neutron Diffraction Pattern Collected at 3.7 (1) GPa and 300 Ka formula P−T conditions crystal system, space group strukturbericht designation cell content cell parameters [Å] cell volume [Å3] density [g·cm−3] Pb Wyckoff site S Wyckoff site dPb−S [Å] dPb−Pb [Å] Rwp (%), χ2

Figure 2. Observed (cyan line) and calculated (dark and orange lines) neutron diffraction patterns for orthorhombic PbS. The observed pattern was collected at 3.7 GPa (see Figure 1c). The calculated patterns are based on Cmcm (B33) and Pnma (B16) orthorhombic structures. The structural parameters for Cmcm used in simulations are listed in Table 1. For B16, simulations are performed by using lattice parameters of a = 11.1288 Å, b = 4.2173 Å, and c = 4.0283 Å. Atomic positions are fixed at Wyckoff sites 4c (x, 1/4, z) with x = 0.1221 and z = 0.3723 for cations and x = 0.3495 and z = 0.5023 for anions, which have commonly been reported for B16-type GeS and SnS.11,41,42.

a

orthorhombic PbS 3.7 (1) GPa, 300 K orthorhombic, Cmcm (No. 63) B33 Pb4S4 a = 4.0283 (3), b = 11.1288 (7), c = 4.2173 (5) 189.063 (4) 8.4057 (6) 4c, (0, y, 1/4), y = 0.3778 4c, (0, y, 1/4), y = 0.1363 2.6882 (2), 2.9203 (3), 3.5121 (3) 3.4410 (3), 4.0283 (4), 4.0743 (5), 4.2170 (3) 6.5, 2.2

See Figure 1c.

positions for Cmcm−PbS are consistent with those reported based on density-functional-theory (DFT) calculations.18 The pressure−volume (P−V) measurements for cubic and Cmcm PbS are illustrated in Figure 4. At ∼2.1 GPa, the cubic-

0.5023), which have commonly been reported in B16-type GeS and SnS (see Figure 2).11,41,42 On the other hand, the calculated pattern for Cmcm is in excellent agreement with the experimental observations. By using ab initio simulations, the pressure dependence of enthalpy differences for Cmcm and Pnma PbS are also computed as shown in Figure 3. The

Figure 4. Room-temperature volume-pressure data of cubic− (open blue squares) and orthor−PbS (solid black circles) obtained from timeof-flight neutron diffraction. The data are fitted to the third-order Birch−Murnaghan equation of state with K′, its pressure derivative of K0, fixed at 4 and 7, respectively, based on the reported values in ref 12 (solid blue line for cubic PbS and black dot line for orthorhombic PbS). Also plotted are experimental observations from ref 12 for comparison purpose (solid cyan circles). Insets are crystal structures of the two phases depicted in polyhedral views. Figure 3. Calculated pressure dependence of enthalpy differences (ΔH) between both orthorhombic and cubic PbS.

orthor transition is accompanied by a ∼3.8% volume collapse, indicating that orthor-PbS is a high-P phase with a higher density. The ambient bulk modulus K0, derived from the second-order Birch−Murnaghan equation of state,43 is 57 (8) GPa for cubic PbS which agrees well with previously reported values (see Figure 4).12,17 Because of the lack of experimental data, the bulk modulus for InI-type PbS cannot be determined accurately in this work; nevertheless, the obtained K0 value of 25 GPa is comparable with previously published values of 25− 34 GPa (see Figure 4).12,17 Also plotted in Figure 4 are P−V data reported by Knorr et al.,12 which is in good agreement with our measurements. Strikingly, the high-density orthorhombic phase is more than ∼50% more compressible than the low-P cubic phase. This anomalous elastic softening is against the common physical intuition and has only sparsely been reported in literature. To confirm such behavior, first-principles calculations were performed on PbS, and the calculation methods are described in the Experimental Section. As shown

calculated phase transition pressures for Cmcm and Pnma phases are 8.5 (1) and 9.8 (1) GPa, respectively, which are much higher than our experimental observation of 2.1(1) GPa and agree well with previous first-principle simulations.12,17 Remarkably, Cmcm is energetically more favorable to be adopted for the orthorhombic phase than Pnma PbS at high pressure. We thus conclude that the orthorhombic PbS is structurally isotypic with indium iodide (InI) adopting the Cmcm (B33) structure. The final refinement results for selected neutron diffraction patterns are shown in Figure 1. The refined crystal structure parameters for Cmcm−PbS are summarized in Table 1. On another note, the obtained figure-of-merit values of the refinements deteriorated with Rwp = 9.0% and χ2 = 4.2 when the atomic positions of Pb and S are exchanged. Coordinates of ypb = 0.3778 and ys = 0.1363 are thus selected for Wyckoff sites 4c(0, y, 1/4) of Pb and S, respectively. The refined atomic 8640

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Cmcm−PbS are more metallic than in the cubic phase. On the other hand, the Pb atoms in the Cmcm phase are 7-foldcoordinated to the S atoms, and it is higher than 6-foldcoordinated {PbS6} octahedrons in cubic PbS (see Figure 4), which is consistent with the pressure-coordination rule.44,45 To take the argument one step further, the phase-transitioninduced elastic softening in PbS may be attributed to such changes in bonding and coordination characteristics at high pressure. Further computational work is warranted to quantify and understand this intriguing phenomenon. Figure 6 shows electrical resistance (R) of PbS as a function of pressure, R(P), at several different temperatures. A

in Figure 5, the calculated P−V data for both phases are consistent with observations within the experimental pressure

Figure 5. Calculated P−V data for both B1 (pink) and B33 (black) PbS based on ab initio simulations. For comparison purpose, the measured P−V data are also plotted (solid blue circles).

ranges. The K0 values, derived from the fit to a third Birch− Murnaghan equation of state,43 are 55 (2) and 24 (2) GPa, respectively, for the cubic and orthorhombic phases, which agree well with our experimental measurements (see Figure 4) and reported in refs 12 and 17. The derived K′, the pressure dependence of K0, however, is substantially different, 7.5 (3) for the orthorhombic PbS and 4.3 (3) for the cubic phase. To take into account the well-known K0−K′ trade-off, we fitted the P− V data for both phases at a fixed value of K′ = 4, and we obtain 57 (2) and 30 (8) GPa, respectively, for the cubic and the orthorhombic phases. Thus, for both fitting schemes our simulations support the experimental finding of phasetransition induced elastic softening. For comparison purpose, the K0 and P−T data are also simulated for Pnma−PbS, which are close to those of Cmcm−PbS (see Supporting Information, Figure S1). The refined structural parameters for cubic− and orthor−PbS at 2.1(1) GPa are listed in Table 2. Notably, three of the four

Figure 6. In situ electrical resistance measurements for PbS. (a) Electrical resistance as a function of pressure at temperatures of 300 K, 423 K, 573 K, 673 K, and 773 K. The resistance data collected at 673 and 773 K are enlarged ten times (×10) to show detail. (b) Cubicorthorhombic phase boundary for PbS determined based on electrical resistance measurements.

remarkable resistance jump is observed in each of the R(P) curves except for the case at 773 K (Figure 6a). Such discontinuous variations are strong indication of pressureinduced cubic-to-orthor phase transition, which is in agreement with previously reported measurements.3,14,16 At 773 K, no visible resistance jump is observed, implying that the cubic-toorthor phase transition does not occur within the experimental pressure range. As discussed above, orthorhombic PbS is more metallic than cubic phase because of its shorter Pb−Pb bonds. However, contrary to what one might expect, the orthorhombic phase exhibits much lower electrical conductivity than the cubic phase as shown in Figure 6a. This is mainly because electrical conductivities in low-symmetry crystals are often lower than in high-symmetry crystals. In fact, depending on symmetry changes, the structural transition induced electrical resistivity jump or drop have both been reported in the literature.46 Compared with cubic PbS, the orthorhombic structure possesses a lower crystal symmetry with a “disordered” atomic arrangement. As a result, electrical resistivity increases abruptly during the cubic-to-orthor transition in PbS. To gain further insight into such behavior, we performed band structure calculations for both B1 and B33 phases of PbS (see Experimental Section). As shown in Figure 7, the two phases show remarkable differences in their band structures and total density of states (DOS) at the Fermi energy level (Ef = 0 eV). The cubic phase is a direct band gap semiconductor because the valence-band top and conduction-band bottom occur at the same L symmetry point (see Figure 7 a). The obtained band gap, Eg, is 0.47(1) eV, which is close to the experimental value

Table 2. Refined Structural Parameters for Cubic and Orthorhombic PbS at 2.1(1) GPa and 300 Ka cubic, B1 P−T conditions structure cell content cell parameters [Å] cell volume [Å3] density [g·cm−3] dPb−S [Å] dPb−Pb [Å] a

2.1(1) GPa, 300 K NaCl-type, Fm3̅m Pb4S4 a = 5.8713 (2) 202.393 (5) 7.852 (4) 2.9360 (2) 4.1516 (3)

orthorhombic, B33 2.1(1) GPa, 300 K InI-type, Cmcm Pb4S4 a = 4.1057 (7), b = 11.2215 (9), c = 4.2272 (7) 194.755 (7) 8.160 (6) 2.7103 (3), 2.9510 (4), 3.5544 (5) 3.4620 (5), 4.1065 (5), 4.1123 (3), 4.2271 (4)

See Figure 1b.

Pb−Pb bonds become shorter upon the transition from cubic− to orthor−PbS. In particular, the nearest distance between two neighboring Pb atoms is only 3.4620 Å, which is 16.6% shorter than that of cubic phase (4.1516 Å) and is even shorter than the interatomic distance in lead metal (∼3.5 Å). The shortest Pb−Pb bond is found in CsCl-type metallic PbS, which is ∼3.29 Å.8,17,18 These evidence indicate that chemical bonds in 8641

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Figure 7. Simulated band structures (upper panel) and total density of state (DOS) (bottom panel) for PbS (a) cubic, B1 phase, (b) orthorhombic, B33 phase. Cyan lines denote Fermi energy level (Ef = 0 eV).

of 0.42 eV at 300 K47,48 and also agrees well with the reported theoretical result.17 Strikingly, the orthorhombic phase is typical of a semiconductor with an indirect band gap of Eg = 1.04(1) eV (see Figure 7 b), similar to that of silicon (Eg = 1.11 eV at 300 K), one of the well-recognized indirect semiconductors.49 Thus, our simulations infer a direct-to-indirect band gap transition in semiconducting PbS, which is primarily responsible for the observed electrical resistivity jump (see Figure 6). Band structures of Pnma-type PbS are also computed (see Supporting Information, Figure S2). Moreover, on the basis of electrical resistance measurements, the phase boundary for PbS can be determined and is plotted in Figure 6b. The thusmeasured transition pressures are slightly higher than those observed in neutron diffraction experiments, which may be attributed to the different pressure calibration methods. To understand the pressure-induced B1→B2 phase transition, crystal structures of B1-, B33-, and B2-type PbS are illustrated in polyhedral views in Figure 8. As shown in Figure 8a, the orthorhombic B33 phase can simply be viewed as a slight translation of trigonal-prismatic coordination along the (110) crystallographic plane in the B1 phase at high pressure. The translation distance is √2a/4, where a is lattice parameter of the B1 phase. For B33 → B2 transition, as shown in Figure

8b, the motion of the next-nearest neighbor Pb atom into {SPb7} coordination (see insets in Figure 4) would initially lead to a distorted {SPb8} coordination in the B33 structure. At further higher pressures, the distorted cubic lattice is eventually converted into regular cubic coordination {SPb8} to form a CsCl-type structure.

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CONCLUSION

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ASSOCIATED CONTENT

In summary, the pressure-induced phase transition in PbS was studied by using time-of-flight neutron diffraction, in situ electrical resistance measurements, and first-principles calculations. The refinements of the neutron diffraction data show that orthorhombic PbS adopts an InI-type, B33 structure with the Cmcm (No. 63) space group . The cubic-to-orthor phase transition starts at 2.1(1) GPa and is accompanied by a ∼3.8% volume collapse. On the basis of first-principles calculations, both cubic and orthorhombic phases are semiconductors, but they exhibit features of direct and indirect band gaps, respectively, with Eg = 0.47(1) and 1.04(1) eV. Phase transition induced elastic softening is observed in PbS and is likely to be associated with enhanced metallic Pb−Pb bonding in the orthorhombic phase. Phase transition also leads to an anomalous drop in electrical conductivity in orthorhombic PbS, which is mainly attributed to the lower crystal symmetry and the enlarged band gap in the Cmcm phase. Based on the refined structure for B33, phase transitions paths for B1→ B33→B2 involve translation of a trigonal prism in the B1 phase and motion of the next-nearest neighbor Pb atom into {SPb7} coordination and subsequent lattice distortion in the B33 phase.

S Supporting Information *

Figure 8. Schematic illustrations of pressure-induced phase transitions in PbS. (a) phase transition between B1 and B33. (b) Phase transition between B33 and B2. Unit cells of the B1 and B33 phases are outlined in red.

Further details are given in Figures S1−S2. This material is available free of charge via the Internet at http://pubs.acs.org. 8642

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AUTHOR INFORMATION

Corresponding Author

*E-mail: (D.H.) [email protected]. E-mail: (Y.Z.) [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work has partly benefited from the use of the Lujan Neutron Scattering Center at Los Alamos Neutron Science Center, which is funded by the U.S. Department of Energy′s Office of Basic Energy Sciences. This work is also supported by UNLV High Pressure Science and Engineering Center (HiPSEC), which is a DOE NNSA Center of Excellence operated under Cooperative Agreement DE-FC5206NA27684, and UNLV start-up funding to Y.Z. We thank support from the China 973 Program (Grant 2011CB808205), and the National Natural Science Foundation of China (Grant 11027405). We thank X. Zhou for the electrical resistance measurements.

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